Method of activating per-compounds and solid activated per-compound compositions

ABSTRACT

WHEREIN AT LEAST TWO OF R1, R2, R3 and R4 are acyls of organic carboxylic acids having from two to eight carbon atoms and the remainder of R1, R2, R3 and R4 are members selected from the group consisting of hydrogen, alkyl having from one to eight carbon atoms, phenyl, phenylalkyl having from seven to eight carbon atoms and acyls of organic carboxylic acids having from two to eight carbon atoms, and novel acylated glycolurils.   The method of activating aqueous solutions of per-compounds utilizing an activator acylated glycoluril and solid activated compositions of solid per-compounds and an activator acylated glycoluril, said activator acylated glycoluril having the formula

United States Kuhling et al.

atent H 1 1 Feb. 6, 1973 METHOD OF ACTIVATING PER- COMPOUNDS AND SOLID ACTIVATED PER-COMPOUND COMPOSITIONS [75] Inventors: Dieter Kuhling, Monheim, Rhineland; Hans-Joachim Heitland, Dusseldorf, both of Germany [73] Assignee: Henkel & Cie GmbH, Dusseldorf- Holthausen, Germany [22] Filed: May 7, 1971 21 Appl. No.: 141,372

Related US. Application Data [63] Continuation-impart of Ser. Nos. 787,597, Dec. 27, l968, abandoned, and Ser. No. 787,628, Dec. 27, 1968, abandoned.

[30] Foreign Application Priority Data Dec. 30, 1967 Dec, 30, 1967 Germany ..H 64 924 Germany ..H 64 923 [56] References Cited UNITED STATES PATENTS 4/1965 Brightetal .I252/99 Slezak eta]. ...260/309.7 Gandon et al ..260/309.7

Primary Examin'erMayer Weinblatt AttorneyHammond & Littell [57] ABSTRACT The method of activating aqueous solutions of percompounds utilizing an activator acylated glycoluril and solid activated compositions of solid per-compounds and an activator acylated glycoluril, said activator acylated glycoluril having the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having from two to eight carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen, alkyl having from one to eight carbon atoms, phenyl, phenylalkyl having from seven to eight carbon atoms and acyls of organic carboxylic acids having from two to eight carbon atoms, and novel acylated glycolurils.

12 Claims, No Drawings METHOD OF ACTIVATING PER-COMPOUNDS AND SOLID ACTIVATED PER-COMPOUND COMPOSITIONS REFERENCE TO PRIOR APPLICATIONS This application is a combination and continuationin-part of our copending patent applications Ser. No. 787,597, filed Dec. 27, 1968, and Ser. No. 787,628, filed Dec. 27, 1968, both now abandoned.

THE PRIOR ART Solid inorganic per-compounds, especially perborates, are known as active substances present in many oxidizing and bleaching agents, which are used for a large number of different purposes, but especially for bleaching and in some cases for the simultaneous washing of textiles. The active oxygen of the inorganic per-compounds is generally only active at temperatures above 70C. and preferably in the range from 80 to 100C. so that only textiles insensitive to temperature can be bleached by means of inorganic per-compounds. Of course, washing agents containing such inorganic per-compounds, and especially perborates, are frequently used for washing textiles sensitive to temperature, generally at temperatures from 30 to 50C., that is, in a range in which the active oxygen present in these washing agents is not yet fully active. The agent is therefore not fully utilized and a part remains unused in the wash liquor.

Aqueous solutions of inorganic per-compounds, especially of hydrogen peroxide or perborates, have been used for a long time as oxidizing and bleaching agents for a large variety of materials. However, as indicated above, for practical purposes the active oxygen released by the per-compounds does not act with sufficient speed until temperatures above 70C., and preferably in the range from 80 to 100C, are reached. Therefore, these bleaching agents cannot be used with materials which are sensitive to temperature. When such materials have to be bleached, this has to be effected at relatively low temperatures.

The literature contains numerous suggestions for making the active oxygen available at temperatures below 70C. by addition of inorganic catalysts or organic activators, but these proposals have not previously been practical.

OBJECTS OF THE INVENTION wherein at leasttwo of R R R and R are acyls of organic carboxylic acids having from two to eight carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen, alkyl having from one to eight carbon atoms, phenyl, phenylallcyl having from seven to eight carbon atoms and acyls of organic carboxylic acids having from two to eight carbon atoms.

A further object of the invention is the obtention of aqueous compositions of per-compounds and acylated glycolurils which are active at temperatures below C. in aqueous solutions.

Another object of the present invention is the obtention of solid, powdery to granular oxidation, bleaching and washing agents comprising a content of a solid inorganic per-compound and an effective amount of acylated glycoluril activators having the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having from two to eight carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen, alkyl having from one to eight carbon atoms, phenyl, phenylalkyl having from seven to eight carbon atoms, and acyls of organic carboxylic acids having from two to eight carbon atoms.

A yet further object of the invention is the obtention of acylated glycolurils having the formula DESCRIPTION OF THE INVENTION The invention relates to the use of certain organic substances as activators for per-compounds when dissolved in aqueous solutions, which enable the minimum temperature needed for a practically effective bleaching and oxidation to be reduced and/or the oxidation process to be accelerated.

The substances to be used as activators for the percompounds according to the invention are acylated glycolurils of the following formula in which at least two of the residues R, to R represent acyl residues of organic carboxylic acids with two to eight carbon atoms, while the other residues represent hydrogen atoms, alkyl or aryl residues with one to eight carbon atoms and/or acyl residues of organic carboxylic acids with two to eight carbon atoms. The acyl residues present in the molecule may be the same or different. Tetra-acylated glycolurils with the same acyl residues of organic carboxylic acids with two to four carbon atoms are preferably used.

The present invention also provides solid, powdery to granular oxidation, bleaching and washing agents comprising a solid inorganic per-compound and, as an activator, the acylated glycolurils having the above formula.

Preferred as activators are acylated glycolurils having the formula wherein at least two of R R R and R are acyls of acids selected from the group consisting of alkanoic acids having two to four carbon atoms, chloroalkanoic acids having two to four carbon atoms and benzoic acid and the remainder of R R R and R are members selected from the group consisting of hydrogen atoms and alkyl having one to eight carbon atoms and said acyls of said acids.

Suitable acyl residues of organic carboxylic acids having from two to eight carbon atoms are, for example, alkanoyls, such as acetyl, propionyl, butyryl, etc; haloalkanoyls, such as monobromoacetyl and preferably chloroalkanoyls such as monochloroacetyl, dichloroacetyl, trichloroacetyl, etc.; nitriloacetyl, benzoyl and toluyl which may be substituted with nitro groups or halogen atoms such as chlorobenzoyl, nitrobenzoyl, chlorotoluyl and nitrotoluyl; methoxybenzoyls; and nitrilobenzoyls. Suitable alkyls having one to eight carbon atoms are, for example methyl, ethyl, etc.

Tetraacetylglycoluril and its preparation are known. It is obtained by acetylating glycoluril with acetic acid anhydride. The other acylated glycolurils can be prepared in an analogous way by reacting the glycoluril with the corresponding carboxylic acid anhydrides, carboxylic acid chlorides or carboxylic acid esters. Apart from tetraacetyl-glycoluril, the activators to be used according to the invention are new chemical substances.

LII

Among the preferred acylated glycoluril can be mentioned the following: tetraacetyl-glycoluril (m.p.233- 240C.), tetrapropionyl-glycoluril (m.p. 144-l46C.), tetrabutyryl-glycoluril, 1,3-dimethyl-4,6-diacetylglycoluril, l-methyl-3,4,o-triacetyl-glycoluril (m.p. l79-180C.), 1,4- diacetyl-3,-dipropionyl-glycoluril (m.p. l44l46C.), l,3-dimethyl-4-acetyl-6-propionyl-glycoluril, 3,6-diacetyl-l ,4-dibenzoyl-glycoluril (m.p. 244249C.), l,4-diacetyl-3,6-dibutyrylglycoluril (m.p. l44-149C.). The alkyl and aryl substituted glycolurils may be produced by condensation of glyoxal with the alkyl or aryl substituted ureas. Any of the above acylated glycolurils may be substituted for the tetraacetyl-glycoluril and tetrapropionylglycoluril utilized in the examples with comparable activation of the active oxygen, taking into account the fact that a larger amount of a diacylated or triacylated glycoluril must be utilized in replacement of a tetraacylated glycoluril.

The per-compounds to be activated in aqueous solution can be any type of inorganic or organic per-compound which will release active oxygen in an aqueous solution. For economic reasons, the per-compounds preferably utilized are inorganic peroxides, inorganic per-acids, inorganic peroxyhydrates and products of the addition of hydrogen peroxide with inorganic and organic compounds.

Of the peroxides to be activated, hydrogen peroxide is of the greatest practical importance. It may be used as such, but may also be used in the form of its mostly solid peroxyhydrates or products of addition with inorganic and organic compounds. The latter include, for example, the products of addition of hydrogen peroxide to urea or melamine, and examples of the peroxyhydrates are the perborates, perortho-, perpyro-, and perpoly-phosphates, percarbonates and persilicates. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts. The activators according to the invention, however, may also be used together with true per-acids, such as for example, Caros acid (peroxymonosulfuric acid, H 80 or peroxydisulfuric acid (P1 8 0 or their salts.

Each acyl residue present in the acetylated glycoluril activator is able to activate an active oxygen atom of the per-compound used. Therefore, in theory, the activator and per-compound should be used in equivalent amounts for complete activation of the active oxygen present. In practice, however, satisfactory effects are attained in many cases even with substantially smaller amounts of activator, while on the other hand, the activator may also be used in relatively large excess. It has been found that the activating effect can occur with addition of very small amounts of 0.04, preferably 0.1 acyl groups per atom of active oxygen. Excesses, however, may be utilized up to 6 acyl groups per atom of active oxygen. Preferably 0.5 to 4, more particularly 0.5 to 2, acyl groups are supplied per atom of active oxygen.

The acceleration of the bleaching and oxidizing processes is shown both at low temperatures in the range from 20 to70 and preferably from 30 to 60C., and at temperatures above these limits, which may go up to C. Depending upon the problem to be solved, it is possible for the technician, when using the activa- 5 to 40 percent, preferably l2 to 30 percent, by

weight of surface active compounds or combinations of surface-active compounds, said surfaceactive compounds comprising:

to 100 percent, preferably 25 to 65 percent, by

weight of surface-active compounds of the sulfonate and/or sulfate type,

0 to 100, preferably 5 to 40 percent, by weight of non-ionic surface-active compounds,

0 to 100 percent, preferably to 50 percent, by

weight of soap,

0 to 6 percent, preferably 0.5 to 3 percent, by

weight of foam stabilizers,

0 to 8 percent, preferably 0.5 to 5 percent, by

weight of foam inhibitors;

10 to 82 percent, preferably 35 to 75 percent, by weight of builders, at least a part of these builders having an alkaline reaction and the amount of toneutral reacting builders preferably constituting 0.5 to 7 times, and especially 1 to 5 times, that of the total combination of surface-active compounds present;

10 to 50 percent, preferably l5 to 35 percent, by

weight of the combination according to the invention, of solid inorganic per-compounds, especially perborate, and acylated glycoluril, and, optionally, a stabilizer for the per-compound, but in which the amount of this combination is such that the content of active oxygen is from 1 to 4 percent, preferably 1.5 to 3.5 percent by weight of the total bleaching washing agent;

0 to percent, preferably 2 to 12 percent, by weight of other washing agent components or additives, such as, for example, dirt carriers, brighteners, enzymes, perfumes, dyestuffs and water.

The activators may be admixed as powder or granulates with the other components of the oxidizing, bleaching or washing agent. If, as is generally customary in the washing agent industry, a washing agent powder not containing per-compounds has been prepared by spray drying, this is preferably then mixed with the per-compound and the activator, whereby the powder is maintained at room temperature on addition of the activator.

When the solid inorganic per-compound and the acylated glycoluril activators are to be added to the spray dried washing agent powder, they can be added as a stable composition of the two ingredients with, optionally, a stabilizer for the per-compound, in the proportions given above.

The particles of the acylated glycoluril activators incorporated in the oxidizing, bleaching or washing agent, may also be coated with water-soluble high molecular weight organic substances or water-insoluble high molecular weight organic substances preferably capable of swelling in water. Suitable covering substances are, for example, gelatine, methyl cellulose, hydroxyethyl cellulose, ethyl cellulose and carboxymethyl cellulose. Solid water-soluble polyglycol ethers, including different types of solid, non-ionic surface-active substances, such as, for example, the later described polyethylene glycolpolyrpopylene glycolmixed ethers, are also utilizable for this purpose.

The products according to the invention may be used in a large variety of fields as oxidizing and bleaching agents. A preferred field is in the bleaching and bleaching-washing of fibers of natural or synthetic origin. Besides the textiles of cotton, regenerated cellulose or linens to be treated chiefly at temperatures of from to C, with a concentration of usually from 1 gm per liter to 10 gm per liter, preferably from 2 gm per liter to 7.5 gm per liter of bleaching and washing agent in aqueous solution, the so-called easy-care textiles especially can be washed and/or bleached with the agents according to the invention. Among the easy-care textiles are those consisting of cotton with a high finish or synthetic fibers, such as, for example, of polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers, or containing at least 30 percent of these. Correspondingly treated synthetic fiber-cotton blended fabrics are especially to be mentioned here as easy-' care" textiles, sometime also called non-iron".

Suitable temperatures for bleaching or washing these easy-care textiles are from 20 to 70C., preferably from 30 to 60C. Also the above-named textiles, usually bleached between 70 to l00C., may, with the use of products of the invention, be bleached at lower temperatures whereby also here a combination of lowtemperature bleaching and high-temperature bleaching is possible, particularly if the activator is used in a deficient amount, so that after consumption of the activator still sufficient amounts of active oxygen are available to be activated thermally. The high degree of whiteness obtainable according to the invention also at these temperatures is particularly advantageous in connection with simultaneous or subsequent treatment of the textiles with optical brighteners.

Of the solid inorganic per-compounds, the compounds having a neutral-to-alkaline reaction in aqueous solution, especially the perborates, are of particular practical interest.

Among the various perborates, sodium perborate tetrahydrate (NaBO -H O -3H O) is of great practical importance. Dehydrated perborates, i.e., up to the approximate composition NaBO -H O may also be used partly or wholly in its place. Finally, borates NaBO -l-l 0 containing active oxygen, in which the proportions NQTDTEG; is less than 05:1 and is preferably in the range from 0.4 to 0.15:1, and in which the proportions H O zNa is in the range from 0.5-4:1, are also useful. These products are described in German Pat. No. 901,287 and in U.S.Pat. No. 2,491,789. I

The perborates may be wholly or partly replaced by other inorganic per-compounds, especially by peroxyhydrates, as for example, the peroxyhydrates of orthopyroo r poly-phosphates and also the carbonates. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts.

The oxidizing, bleaching and washing agents according to theinvention may contain the usual water-insoluble or water-soluble stabilizers for per-compounds in amounts up to 10 percent, preferably from 0.5 to 8 percent by weight.

The various magnesium silicates are suitable as water-insoluble stabilizers for per-compounds. These are usually precipitated products which are formed on purifying aqueous solutions of alkali metal silicates with solutions of magnesium salts. The ratio MgOzSiO tors according to the invention, either to reduce the temperature of treatment and/or to shorten the time of treatment, the temperature remaining the same. Finally, a low and a high temperature bleach can also be combined in one operation. In such cases it may be advantageous to add less than the theoretical amounts of activator; then at low temperatures only a part of the active oxygen present is activated, and the remainder is available for the bleaching at elevated temperatures.

The conditions to be maintained during operation with the activators according to the invention, such as for example, the concentration of the peroxide, temperature, pH value and time of treatment, depend substantially on the substance to be oxidized and/or bleached, and in some cases on the carrier material on or in which the substance to be bleached is present. The usually aqueous oxidizing or bleaching liquids may contain 5 mg to 500 mg, preferably mg to 250 mg per liter of active oxygen and have a pH value from 7 to 12, preferably from 7 to l 1.5, and especially from 8 to 10.5.

As previously stated, aqueous solutions of per-compounds and acylated glycoluril activators, optionally with other ingredients as indicated below may be utilized. These aqueous solutions preferably contain sufficient per-compounds to give a concentration of from 5 mg to 500 mg, preferably 10 mg to 250 mg per liter of active oxygen and sufficient acylated glycoluril activators to provide from 0.04 to 6, preferably 0.5 to 4 acyl residues of the acylated glycoluril per active oxygen atom.

The activators, according to the invention, may be used wherever per-compounds, especially hydrogen peroxide or perborates, have previously been used as oxidizing and/or bleaching agents. This applies, for ex ample, to the bleaching of oils, fats and waxes, to cosmetic skin or hair treatment, in disinfection or sterilization, in passivation of aluminum or other light metal surfaces, and especially in the bleaching of fibrous substances of all kinds.

The desired pH value is adjusted by addition of acid-, neutralor alkaline-reacting substances, possibly by buffer mixtures, and particularly are additives which have also been co-employed in a corresponding, formerly customary, treatment.

These frequently include the surface-active substances which serve to decrease the surface tension of the aqueous oxidizing or bleaching liquid, such as for example, soap or known synthetic detergents of anionic, non-ionic, amphoteric or cationic nature. When working in the alkaline range, alkaline substances may be added as well as inorganic or organic complex-forming compounds, especially complex forming compounds suitable for binding the so-called hardness-producing substances in water or heavy metals which may possible be present.

As indicated, the present invention also provides solid, powdery to granular oxidation, bleaching and washing agents comprising a solid inorganic per-compound and the activator acylated glycolurils.

The minimum temperature necessary for an effective oxidation or bleaching with solid inorganic per-compounds is reduced by the addition of these acylated glycolurils and/or the oxidation or bleaching process is accelerated. The advantages of the presence of the acylated glycolurils are not, however, restricted to the activation of the per-compounds present. Owing to the high melting point of the acylated glycoiurils, which in the case of tetrapropionyl-glycoluril is in the region of 144 to l46C. and in the case of tetraacetyl-glycoluril is in the region of 236 to 238C, the oxidizing, bleaching, and washing agents according to the invention are very stable on storage. Even with relatively long storage times, they show a very low loss of active oxygen and at the same time only a small decline in the oxygen activation. This is particularly valid when the activators are protected by a protective coating or cover from contact with the other ingredients of the washing agent, above all from the alkaline ingredients and the per-compounds.

in the oxidizing, bleaching and washing agents the combination according to the invention of solid inorganic per-compounds, activator and possible a stabilizer for the per-compound, constitutes from 10 to 100 percent of the total composition. In theory, acyl residue present in the acylated glycoluril activator is able to activate an active oxygen atom of the per-compound used. In practice, however, especially when using tetraacylated glycolurils, at first two of the acyl groups react with the active oxygen atom, whereas the remaining acyl groups react one after the other with increasing temperature. Therefore, in theory, the activator and per-compound may be used in equivalent amounts for complete activation of the active oxygen present. In practice, however, satisfactory effects are attained in many cases even with substantially smaller amounts of activator, while on the other hand, the activator may also be used in relatively large excess.

It has been found that the activating effect can be released already with slight addition amounts of, for example, 0.04, preferably of 0.1, acyl groups per atom of active oxygen. However, excesses may be utilized which go up to 6 acyl groups per atom of active oxygen. Preferably 0.5 to 4, and more particularly 0.5 to 2 acyl groups, are utilized per atom of active oxygen.

The products of the invention can be employed in the most varied technical fields anywhere it is important to activate oxygen in order to oxidize. It performs its oxidizing effect already at temperatures of 20 to 70C., preferably 30 to C. Examples for such application fields are the cleaning of instruments, apparatus, pipe lines and vessels of wood, plastic, metal, ceramic, glass, etc., in the industry or in technical plants; the cleaning of furniture, walls, the dishwashing in the household; and particularly the bleaching or laundering of textiles of any kind in industry, in commercial laundries and in the household. The low-temperature bleaching with the use of chemically activated oxygen may also be combined with a high-temperature bleaching in which the oxygen is activated thermally. There is, therefore, the possibility in the industry, in the commerce and in the household, dependent upon the problems to be solved, by the use of the activators of the invention either to lower the treatment temperature and/or to shorten the treatment at the same temperature, or, as already mentioned, to combine a low-temperature and a high-temperature bleaching.

Finally, in a preferred embodiment the invention relates to a bleaching washing agent comprising:

However, the surface-active compounds may also be combined with known foam inhibitors which are not surface-active compounds. These may possibly include N-alkylated aminotriazines, possibly containing chlorine, which are obtained by reacting one mol of cyanuric acid chloride with two to three mol of a monoand/or di-alkylamine with six to 20, preferably eight to 18 carbon atoms in the alkyl residue. Paraffins, halogenated paraffins, and aliphatic C to C ketones can also be used as foam inhibitors, especially in combination with soaps.

These foam inhibitors can also be combined with known foam stabilizers and washing agents are thus obtained which still foam in the middle temperature range up to, for example, 65C., but develop less and less foam when utilized at higher temperatures.

Similar effects are obtained by a choice of soaps, especially when these are combined with anionic and/or non-ionic surface active compounds. Soaps with, for example, 12 to 18 carbon atoms in the fatty acid residue show a certain foam inhibiting effect which, however, is often not sufficient when the washing agent has to be used in washing machines at temperatures from 60 to 100C. In such cases a powerful foam-inhibition action is obtained in the case of synthetic anionic, amphoteric and non-ionic surfaceactive compounds by soaps from fatty acid mixtures which consist of at least 50 percent of fatty acids with 16 to 30 carbon atoms and at least 3, preferably more than percent of fatty acids with 20 or more carbon atoms, while saturated fatty acids containing at least 16 carbon atoms preferably constitute at least 50 percent of the total soap fraction.

Weakly acid, neutral and alkaline-reacting inorganic or organic salts, especially inorganic or organic complex-forming compounds, are useful as the builders present in the products according to the invention.

Weakly acid, neutral or alkaline-reacting salts useful according to the invention are, for example, the bicarbonates, carbonates or silicates of the alkali metals, mono-, dior tri-alkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as complex forming compounds, alkali metal sulfates and alkali metal salts of organic, non-surface-active, sulfonic acids, carboxylic acids and sulfocarboxylic acids containing one to eight carbon atoms. These include, for example, water-soluble salts of benzene-, tolueneor xylene-sulfonic acids,

water-soluble salts of sulfoacetic acid, sulfobenzoic acid or the salts of sulfodicarboxylic acids, and also the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Suitable complex-forming builders are the weakly acid-reacting metaphosphates and the alkaline-reacting polyphosphates, especially tripolyphosphate. They may be wholly or partly replaced by organic complex-forming compounds.

The organic complex-forming compounds include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, polyalkylenepolyamine-N-polycarboxylic acids and other known organic complex-forming compounds. Combinations of different complex-forming compounds may also be used. Diand polyphosphonic acids of the following in which R represents alkyl and R represents alkylene residues with one to eight, preferably one to four, carbon atoms, and X and Y represent hydrogen atoms or alkyl with one to four carbon atoms. Carboxymethylenephosphonic acid HOOCCH,PO(OH) is also useful as a complex-forming compound according to the invention. All these complex-forming compounds may be present as free acids, but it is preferred to use then as their alkali metal salts.

In the preparations according to the invention, dirt carriers may also be present, which hold the dirt detached from the fibers suspended in the liquor, and thus prevent greying. Water-soluble colloids of usually organic nature are suitable for this purpose, as for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether-carboxylic acids or ether-sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Watersoluble polyamides containing acid groups are also suitable for this purpose. Furthermore, starch and other than the above-mentioned starch products can be used, such as, for example, degraded starch, aldehyde starches and so on. Polyvinylpyrrolidone is also useful.

The present invention will be further described by way of reference to the following examples. These examples are, however, not to be deemed limitative in any manner.

EXAMPLE 1 Preparation of l,3,4,6-tetraacetyl-glycoluril A suspension of gm of glycoluril in 1.5 liters of acetic acid anhydride was boiled under reflux with stirring, until the glycoluril has completely dissolved. After distilling off the excess aceticacid anhydride and the acetic acid formed in the reaction, the crude tetraacetyl-glycoluril remained. It may be used without further processing, but if desired it can be purified, for example, by recrystallization in the following way.

The crude tetraacetyl-glycoluril was taken up in a little methanol and the solvent was filtered off from the residue remaining undissolved. The residue was recrystallized from a'mixture of 4 parts by volume of methanol and 1 part by volume of ethyl acetate. g (52.8 percent of theory) of tetraacetyl-glycoluril having a melting point of 233 to 240C. were obtained. According to the data in the literature, the melting point is 236 to 238C.

may lie within the range of 4:1 to 1:4, preferably from 2:l to 1:2. A product with a ratio MgOzSiO of 1:1 is chiefly used. These magnesium silicates may be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. Water-containing oxides of tin are also useful as stabilizers. These stabilizers are mostly present in quantities from 1 to 8 percent, preferably from 2 to 7 percent, of the weight of the whole preparation.

The water-insoluble stabilizers may be wholly or partly replaced by water-soluble stabilizers. For this purpose the organic complex-forming compounds described hereinafter are suitable, and the amount used may be from 0.25 to 5 percent, preferably from 0.5 to 2.5 percent, of the weight of the whole preparation, depending upon the strength of the complex formed.

A specified pH value is often maintained in an oxidizing, bleaching and/or washing process. Therefore, weakly acid, neutral or alkaline-reacting substances are frequently added to the oxidizing, bleaching and washing agents according to the invention in order that the agents may have the desired pH value in aqueous solution. For a 1 percent solution of the preparation, this pH will generally lie in the range from 7 to 12, the fine washing agents being generally adjusted to a neutral-toweakly alkaline pH (pH 7 to 9.5), while the high temperature washing agents have a more strongly alkaline reaction (pH 9.5 to 12, preferably 10 to 11.5). Known, neutral to alkaline reacting builders are suitable for this purpose.

The anionic, amphoteric or non-ionic surface-active compounds possibly present in the products according to the invention contain in the molecule at least one hydrophobic residue containing eight to 30 carbon atoms and an anionic or non-ionic water-solubilizing group. The hydrophobic residue may be aliphatic or alicyclic, preferably saturated in nature, and may be combined with the water-solubilizing groups directly or through intermediate members. Suitable intermediates members are, for example, benzene rings, carboxylic acid ester groups or carbonamide groups, ethylene glycol or propylene glycol residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18 carbon atoms, but deviations from this preferred carbon range are possible depending on the nature of the surface-active compound in question.

Soaps are useful as anionic detergents which are derived from natural or synthetic fatty acids, and possibly also from resin or naphthenic acids.

Of the synthetic anionic surface-active compounds, the sulfonates and sulfates are of special practical importance.

The sulfonates include, for example, the alkylaryl sufonates, especially the alkylbenzene sulfonates, which may be obtained preferably from straight-chain aliphatic hydrocarbons having nine to 15, preferably 10 to 14, carbon atoms, by chlorination and alkylation of benzene or, from corresponding olefins with terminal or non-terminal double bonds, by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Furthermore, aliphatic sulfonates are of interest, such as, for example, those obtainable from preferably saturated hydrocarbons containing eight to 18 and preferably 10 to 16 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen, and conversion of the products thereby obtained into the sulfonates. Furthermore, mixtures of alkenesulfonates, hydroxyalkenesulfonates and hydroxyalkanesulfonates, such as are obtained, for example, from terminal C -C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonated products, are utilizable as aliphatic sulfonates. In the aliphatic sulfonates so prepared, the sulfonate group is frequently attached to a secondary carbon atom. However, by reacting terminal olefins with bisulfite, sulfonates with primary or terminal sulfonate groups may be prepared.

Esters of a-sulfo-fatty acids with monoor polyhydric alcohols containing one to four, preferably one or two, carbon atoms also belong to the sulfonates to be used according to the invention.

Suitable surface-active compounds of the sulfate type are fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type can also be prepared from C C18 olefins with terminal or non-terminal double bonds. Furthermore, this group of surface-active compounds includes sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfated products of ethoxylated and/or propoxylated fatty alcohols, alkylphenols with eight to 15 carbon atoms in the alkyl residue, fatty acid amides, fatty acid alkylolamides and so on, where 0.5 to 20, preferably one to eight, and especially 2 to 4 mols of ethylene oxide and/or propylene oxide are added on to 1 mol of the said compounds to be ethoxylated and/or propoxylated.

Further utilizable sulfonates are the fatty acid esters of hydroxyethanesulfonic acid and dihydroxypropanesulfonic acid, the fatty alcohol esters of lower aliphatic or aromatic sulfo-monoand sulfo-di-carboxylic acids containing one to eight carbon atoms, as well as the condensation products of fatty acids with aminoethanesulfonic acid.

The washing agents according to the invention may also contain surface-active synthetic carboxylates, for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and also the condensation products of fatty acids with aminocarboxylic acids, for example, of glycocoll or sarcosine, or with albumin hydrolysates.

The foaming properties of the washing agents according to the invention may be increased or reduced by suitable combinations of different surface-active compounds. Among others the products of addition of propylene oxide to the above-described non-ionic polyethyleneglycol-ethers are marked by low foaming properties. By varying the number of ethylene glycol and propylene glycol residues present in the molecule, products with a great variety of turbidity points can be prepared. At temperatures above their turbidity points, these non-ionics act as foam inhibitors on other nonionics. They can, therefore, be used together with other non-ionics in the combinations of surface-active compounds according to the invention, and also in combination with surface-active compounds other than the non-ionic component in the already mentioned combinations from sulfates and/or sulfonates, soaps and non-ionics.

In a second experimental series the activation of tetraacetylglycoluril and tetrapropionylglycoluril was determined; the working conditions deviated from the above-described in the following points:

The activator amount was only 1 m mol/l, corresponding to 1 acyl radical per active oxygen atom. No chemicals for reducing the pH were added; the experimental temperature was 30C. The results obtained are found in the following Table IV.

TABLE IV From the above, it can be seen that the extent of activation is dependent upon the pH, the temperature, the amount of the activator used and upon the nature of the acyl radical present. Thus, with tetraacetylglycoluril already at the start of the experiment, high degrees of activation are obtained, with tetrapropionylglycoluril the degrees of activations are higher near the end of the experiment.

EXAMPLES OF SOLID OXIDATIVE COMPOSITIONS In the production of the preparations described in the following examples, both tetraacetyl-glycoluril and tetrapropionyl-glycoluril were used as activators. A difference was to be observed between the two in that the tetraacetyl-glycoluril showed the maximum degree of activity immediately after dissolving the preparation in water, which activity remained over a certain period dependent on the temperature of treatment chosen. In the case of tetrapropionyl-glycoluril, the amount of activated oxygen rose slowly after the preparation was dissolved in water, but after a relatively long treatment period, for example, after 60 minutes at a 60C. bath temperature, the amount of active oxygen still present was greater than in the case of tetraacetyl-glycoluril.

The two products, therefore, differ in the progress of activation per unit time, and it is possible to select an activator, the action of which is optimal for the purpose in question. If it is a question of attaining a maximum activation in the shortest time possible after dissolving the product in water, tetraacetyl-glycoluril will be chosen. This applies for products, for example, which are used in laundering for after-bleaching.

The perborate" mentioned in the following examples is the commercial product of the approximate composition NaBO -3H O. All percentages given are percents by weight.

EXAMPLE 7 A mixture of 50 percent of fine-grained perborate" and 50 percent of acylated glycoluril activator was found to be suitable as an after-rinsing agent for washed laundry. 5 percent of the perborate may be replaced by MgSiO with excellent results.

EXAMPLE 8 An after-rinsing agent for washed laundry, which at the same time may dissolve or loosen fiber incrustations, especially calcereous incrustations, had the following composition:

30% perborate 20% sodium hydroxyethanediphosphonate 15% Na SO I 35% acylated glycoluril activator.

Here also 5 percent of MgSiO could be incorporated and the Na SO content reduced accordingly.

EXAMPLE 9 A bleaching washing adjuvant, which may be used in the preliminary or main washing operation in an industrial laundry, possibly together with detergent substances and/or complex-forming compounds, especially together with sodium tripolyphosphate, was prepared in the following way.

A mixture of 30 parts by weight of perborate, 25 parts by weight of sodium tripolyphosphate and 5 parts by weight of MgSiO was sprayed with 10 parts by weight of finely dispersed water in a moving granulating dish. During and after the spraying with water, cold air was'passed over the moving material so that, as the water was absorbed, the heat of hydration evolved was removed. 30 parts-by weight of the acylated glycoluril activator were then admixed therewith.

EXAMPLE 10 A mixture of 15 parts by weight of perborate, 60 parts by weight of a voluminous sodium EXAMPLE 1 1 A washing agent removed from the spray-drying tower, after cooling, was divided into three portions. From these, by mixing with perborate" and in some cases tetracetyl-glycoluril, and sodium sulfate, three washing agents A, B and V were prepared with the composition given below, of which the washing agent V is to be regarded only for comparative purposes. The alkylbenzene sulfonate (ABS) used was a commercial straight-chain alkylbenzene sulfonate, the alkyl chain of which contained an average of 12 carbon atoms. The alkylbenzene sulfonate and the soap were present as the sodium salts. CMC was carboxymethyl cellulose present as the sodium salt.

TABLE V By Weight of Component As may be seen, the analysis data calculated for the composition C, 1-1 N,O agreed well with the figures found:

Calculated: C 46.40%; H 4.52%; N 18.05%

Found: C =46.36%; H 4.97%; N 18.12% Moreover, infra-red and NMR spectra showed the characteristic bands for tetraacetyl-glycoluril.

EXAMPLE 2 In an analogous way, 82 g of tetrapropionyl-glycoluril having a melting point of 144 to 146C. were obtained by acylating 100 g of glycoluril in 1.5 liters of propionic acid anhydride and recrystallizing the reaction product from isopropanol. This corresponded to a theoretical yield of 31.5 percent. The analysis data found agreed well with the figures calculated for the composition C, H N.,O

Calculated: C 52.50%; H 6.06%; N 15.32%

Found: C 52.64%; H 6.19%; N 15.61% Moreover, the molecular weight of 358.7 found by osmosis in acetone agreed with that calculated (366.38). Infra-red and NMR spectra showed the characteristic bands to be expected for tetrapropionyl-glycoluril.

Other acylated glycolurils can be produced comparably.

EXAMPLES 2 AND 4 The usefulness of the activators according to the invention was demonstrated by the following experiments:

Solutions which contained 0.615 gm of NaBO H O 3H O (4 mMol) and 2.5 gm of Na P O -lOH O per liter, after addition of4 mMol of activator, were heated to 45 and 60C. respectively and maintained at the said temperature with stirring during the whole experiment. At certain intervals of time, 100 ml samples were removed by pipette, immediately added to a mixture of 250 gm ofice and ml of glacial acetic acid, and then, after addition of about 0.35 gm of potassium iodide, were titrated with 0.1 N sodium thiosulfate solution using starch as an indicator.

Under the experimental conditions indicated, 8.0 ml of thiosulfate solution were consumed with a 100 percent activation of the peroxy-compound peroxy-compound The thiosulfate consumed and the percentage amount of activated peroxy compound are given in Tables 1 and 11. Table for Example 3:

TABLE 1 Activation of perborate with tetraacetyl-glycoluril.

Table for Example 4:

TABLE II Activation of perborate with tetrapropionyl-glycoluril Sample Activation obtained taken at 45C at 60C after 1 ml 0 ml 0 Minutes 0. 1 N activated 0.1N activated Na S,O, 1 121 5 0, x I 2.33 29.2 4.33 54.2 5 6.07 76.0 6.11 76.5

As will be perceived, when tetraacetyl-glycoluril is used, the maximum degree of activation is reached after a time, according to the experiment, of only 1 minute, and this is maintained in practice over a certain period irrespective of the temperature chosen. The subsequent falling off of the values is due to the spontaneous decomposition of the peracetic acid first formed. 1n the case of tetrapropionyl-glycoluril, the amount of activated oxygen increases more slowly, but in this case the amount of active oxygen still present after 60 minutes at 60C. is greater than in the case of tetraacetyl-glycoluril. The products therefore differ in the progress of the activation per unit time and it is possible to select an activator, the action of which is optimal for the bleaching or oxidizing process in question.

EXAMPLES 5 AND 6 Solutions which contained 620 mg/] of a commercial sodium perborate tetrahydrate with about 94 percent by weight active oxygen (4 mg-atom/l active oxygen) and 2.5 gm/] Na,P O -l01-1 O, were after addition of 620 mg/l tetraacetyl-glycoluril (2 mMol/l, corresponding to 2 acetyl radicals per active oxygen) kept at 20C. under constant stirring. 1n definite time periods ml were pipetted off, immediately put on a mixture of 250 gm ice and 15 ml glacial acetic acid and subsequently, after addition of about 0.35 gm potassium iodide, titrated with 0.1 N sodium thiosulfate solution and starch as indicator. The pH of this solution, measured immediately after addition of the tetraacetylglycoluril, was 10.35; in two parallel experiments, solution were processed whose pH-values were adjusted by the addition of borate and hydrochloric acid, or of boric acid, potassium chloride and sodium hydroxide to 8.20 and 10.05.

Under the experimental conditions indicated for a 100 percent activation of the peroxy-compound used about 8.0 ml thiosulfate solution are consumed. In Table 111 the percent activation is calculated from the theoretical maximum consumption and the actual use of thiosulfate solution.

TABLE VI Composition of the pl-l-value degree of whiteness washing agent after bleaching at after bleaching at 45C 60C 45C 60C 100% basic washing agent 9.70 9.70 67.7 70.0 25 TAGU 8.55 8.15 82.5 86.3 15 TAGU 8.85 8.65 80.9 76.9 TAGU 9.30 9.30 77.7 82.5 1 TAGU 9.60 9.60 70.5 74.2 0.5 TAGU 9.65 9.65 67.1 73.4 100% basic washing agent 9.70 9.70 66.8 69.5

25 TAGU 59.0% N co, 10.10 10.00 83.3 87.3 15 TAGU 35.4% Na,CO;, 9.90 82.7 86.7

5 TAGU 11.8% Na CO; 9.85 9.75 78.8 84.0

1 TAGU 2.36% Na,CO;, 9.75 9.70 70.1 78.0

0.5 TAGU 1.18% Na,CO 9.75 9.70 66.9 76.0

The pH-value determined after washing drops with rising TAGU-addition, caused by the splitting-off of acetyl groups. This lowering of the pH is undesirable both for the bleaching and, above all, for the removal of pigment dirt. It is recommended to equalize the dropping of the pH by addition of sodium carbonate. This has been done in the second test series: the improvement of the bleaching effect at a higher pH is obvious.

The bleaching textile treating agents described in the above examples were also prepared by substituting of the sodium perborate tetrahydrate with sodium perborate monohydrate of the approximate composition NaBo,-H,,,,",. These bleaching textile treating agents contained at the same amount of perborate added, a higher content of active oxygen.

The above compositions may be substituted by the other named acylated glycolurils in place of tetraacetylglycoluril or tetrapropionyl-glycoluril without effecting the activation of the active oxygen.

The preceding specific embodiments are illustrative of the practice of the invention. It is apparent, however, that other expedients known to those skilled in the art or discussed herein, such as the use of the other named acylated glycolurils, may be employed without departing from the spirit of the invention.

We claim:

1. The method of activating aqueous solutions of percompounds selected from the group consisting of hydrogen peroxide and water-soluble peroxyhydrates containing from 5 mg to 500 mg per liter of active oxygen, said solution having a pH of from 7 to 12 and a temperature of from 20 to 70C. which consists essentially of incorporating in said aqueous solution an activator acylated glycoluril having the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having from two to eight carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, toluic acid, nitrotoluic acid, halotoluic acid, methoxybenzoic acid and nitrilobenzoic acid, and the remainder of R R R and R are members selected from the group consisting of hydrogen atoms, alkyl having from one to eight carbon atoms, and said acyl of organic carboxylic acids having from two to eight carbon atoms, said acylated glycoluril being incorporated in-said aqueous solution in an amount sufficient that from 0.04 to 6 acyls in said acylated glycoluril are present per active oxygen atomin said aqueous solution.

2. The method of claim 1 wherein said aqueous solution has a pH offrom 7 to 11.

3. The method of claim 2 wherein said aqueous solution has a pH offrom 8 to 10.5.

4. The method of claim 1 wherein said acylated glycoluril is incorporated in said aqueous solution in an amount sufficient that from 0.5 to 2 acyls in said acylated glycoluril are present per active oxygen atom in said aqueous solution.

5. The method of claim 1 wherein said activator acylated glycoluril is tetraacetyl-glycoluril.

6. The method of claim 1 wherein said activator acylated glycoluril is tetrapropionyl-glycoluril.

7. Solid, powdery to granular oxidation compositions consisting essentially of a water-soluble solid inorganic per-compound in the form of its alkali metal salt and an acylated glycoluril activator having the formula wherein at least two of R, R R and R are acyls of organic carboxylic acids having from 2 to 8 carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, toluic acid, nitrotoluic acid, halotoluic acid, methoxybenzoic acid and nitrilobenzoic acid, and the remainder of R R R and R, are members selected from the group consisting of hydrogen atoms, alkyl having from one to eight carbon atoms, and said acyl of organic carboxylic acids having from two to eight carbon atoms, said acylated glycoluril being present in an amount sufficient that from 0.04 to 6 acyls in said acylated glycoluril are present per active oxygen atom in said per-compound.

8. The solid, powdery to granular oxidation compositions of claim 7 wherein said acylated glycoluril is present in an amount sufficient that from 0.5 to 2 acyls in said acylated glycoluril are present per active oxygen atom in said per-compound.

9. The solid, powdery to granular oxidation compositions of claim 7 wherein said R R R and R are the same acyls of alkanoic acids having from 2 to 4 carbon atoms.

10. The solid, powdery to granular oxidation compositions of claim 7 wherein said activator acylated glycoluril is tetraacetyl-glycoluril.

in the Washing Agent Component B V Alkylbenzene sulfonate Nonylphenol 9 EO Soap (saturated C -C fatty acids) Residue Residue Residue 1n the case of washing agent A, 1 mol of acyl residues derived from the activator, and in the case of washing agent B, 3 mols of these acyl residues were present per mol of active oxygen.

Using these washing agents, test swatches of unbleached cotton cloth and cotton swatches with tea and cranberry stains were washed with a concentration of washing agent of 5 gm per liter and a bath ratio of 1:10 for minutes at 45C. in water of 16 German hardness. In the case of washing agent V, a treatment was also carried out at a washing temperature of 90C. for comparative purposes.

The brightness was measured with a reflectance photometer at 460 p. and 620 u and the values obtained were averaged. The following remissions resulted:

Washing agent V 45C 65.6% remission Washing agent A 45C. 72.5% remission Washing agent B 45Cv 76.7% remission Washing agent V 90C. 775% remission In a further experiment the activator was added to the washing liquor prepared from washing agent A in such amount that equimolecular amounts of active oxygen and activator (4 mols of acetyl residues per mol of active oxygen) were present. Then at 45C. a remission of 77.0 percent was obtained.

In a further series of experiments the bleaching actions of washing agent V without addition of activator at 45 and 90C. and with addition to the washing liquor of an amount of tetrapropionyl-glycoluril equivalent to the active oxygen were compared at a washing temperature of 45C. in the above-described way.

The results were as follows:

Washing agent V 45C. 66.6% remission Washing agent V Activator 45C. 78.0% remission Washing agent V 90C. 78.8% remission EXAMPLE 12 By spray drying and subsequent mechanical mixture with a mixture of 66.0 percent of sodium perborate and 34 percent of tetraacetyl-glycoluril, a high temperature washing agent of the following composition was prepared:

12% Alkylbenzene sulfonate (as used in Example 4% Soap (as used in Example 11) 3% C -18 Fatty alcohol 10 E0 38% Na l O 1% Ethylenediaminetetraacetate (Na salt) 1.5 CMC l8 Perborate" 9 Tetraacetyl-glycoluril 0.2 Optical brightener Remainder sodium sulfate and water.

The ethylenediaminetetraacetate present in this washing agent served for the stabilization of perborate against catalytic decomposition by traces of heavy metals which might be in the washing liquor.

EXAMPLE 13 This example demonstrates the bleaching effect which can also be obtained with deficient amounts of tetraacetyl-glycoluril (TAGU). For the carrying out of the bleaching tests a basic washing agent of the following composition was utilized.

7.0 by weight ABS 3.5 by weight soap as in Example 11 4.5 by weight nonionic (fatty alcohol-ethylene oxide deriv.)

40.0 by weight Na P o 1.0 by weight EDTA (ethylenediaminetetraacetic acid-sodium salt) 6.0 by weight Na O-3.3 SiO 1.0 by weight CMC 0.5 by weight Brightener 25.0 by weight Na Bo l-1 0 3 H O 6.0 by weight Sodium sulfate 5.5 by weight Perfume and water All washing tests described below were carried out with washing liquors that contained 6.6 gm/l of this basic washing agent. To this basic washing agent was added the amount of TAGU used each time and, in a second test series, additional sodium carbonate. The various washing agents containing activator were prepared by admixing of each time parts by weight of the basic washing agent with from 0.5 to 25 parts by weight of TAGU and, optionally, with 1.18 to 59 parts by weight of anhydrous sodium carbonate.

As the test material to be bleached, a cotton fabric soiled with red wine (standard soiling of the Federal Material Testing Laboratory, Zurich) was utilized. For the washing tests swatches, 10 X 10 cm, of this testsoiled material were used. In order to adjust as far as possible to practical conditions, clean cotton fabric weighing seven times as much as the test-soiled fabric were added.

The bleaching was carried out in the lauderometer with the use of water of 16 German hardness at a bath ratio of 1:12 and at temperatures of 45 and 60C. The single tests took 15 minutes. However, the vessels with fabrics and the bleaching liquor inside of them were inserted into the launderometer which was preheated to the bleaching temperature. The bleaching liquors were, at that time, still at room temperature.

The bleached textiles were rinsed with water of 16 dH, dried, ironed and measured in the photoelectric Photometer (instrument ELREPHO of the Zeiss Company, Oberkochen) with the blue filter R] 62 (maximum transmittancy at 620 nm), however, with exclusion of the UV-portion of the light. In addition, after laundering, the pH of the washing liquor was determined.

The obtained results can be seen in the following Table V]. In the washing tests without addition of sodium carbonate 0.5 percent TAGU-addition (0.04 acetyl groups/active oxygen) gave only at 60C. an improvement of the bleaching effect (the difference of the 11. The solid, powdery to granular oxidation combelow 70C. which comprises treatingsaid textiles with positions of claim 7 wherein said activator acylated an aqueous solution of the Sa d Solid oXidatlon glycoluril is tetrapropionyl-glycoluril. positions of claim 7 at a temperature below 70C. and

12. A method of bleaching textiles at temperatures above 20C.

an m m =0: 

1. The method of activating aqueous solutions of per-compounds selected from the group consisting of hydrogen peroxide and water-soluble peroxyhydrates containing from 5 mg to 500 mg per liter of active oxygen, said solution having a pH of from 7 to 12 and a temperature of from 20* to 70*C. which consists essentially of incorporating in said aqueous solution an activator acylated glycoluril having the formula
 2. The method of claim 1 wherein said aqueous solution has a pH of from 7 to
 11. 3. The method of claim 2 wherein said aqueous solution has a pH of from 8 to 10.5.
 4. The method of claim 1 wherein said acylated glycoluril is incorporated in said aqueous solution in an amount sufficient that from 0.5 to 2 acyls in said acylated glycoluril are present per active oxygen atom in said aqueous solution.
 5. The method of claim 1 wherein said activator acylated glycoluril is tetraacetyl-glycoluril.
 6. The method of claim 1 wherein said activator acylated glycoluril is tetrapropionyl-glycoluril.
 7. Solid, powdery to granular oxidation compositions consisting essentially of a water-soluble solid inorganic per-compound in the form of its alkali metal salt and an acylated glycoluril activator having the formula
 8. The solid, powdery to granular oxidation compositions of claim 7 wherein said acylated glycoluril is present in an amount sufficient that from 0.5 to 2 acyls in said acylated glycoluril are present per active oxygen atom in said per-compound.
 9. The solid, powdery to granular oxidation compositions of claim 7 wherein said R1, R2, R3 and R4 are the same acyls of alkanoic acids having from 2 to 4 carbon atoms.
 10. The solid, powdery to granular oxidation compositions of claim 7 wherein said activator acylated glycoluril is tetraacetyl-glycoluril.
 11. The solid, powdery to granular oxidation compositions of claim 7 wherein said activator acylated glycoluril is tetrapropionyl-glycoluril. 